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CO2 refrigerant
for Industrial Refrigeration
REFRIGERATION &
aIR CONDITIONING DIVISION
Article
Article
Contents
Page
Introduction................................................................................................................................................................................ 4
Characteristics of CO2.............................................................................................................................................................. 5
CO2 as a refrigerant................................................................................................................................................................... 6
CO2 as a refrigerant in industrial systems......................................................................................................................... 7
Design pressure......................................................................................................................................................................... 9
Safety...........................................................................................................................................................................................10
Efficiency....................................................................................................................................................................................11
Oil in CO2 systems...................................................................................................................................................................11
Comparison of component requirements in CO2, ammonia and R134a systems...........................................12
Water in CO2 Systems.............................................................................................................................................................14
Chemical reactions.........................................................................................................................................................16
Water in Vapor Phase.....................................................................................................................................................16
POE lubricant....................................................................................................................................................................16
PAO lubricant....................................................................................................................................................................16
Removing water......................................................................................................................................................................17
How does water enter a CO2 system?..............................................................................................................................19
Miscellaneous features to be taking into consideration in CO2 refrigeration systems..................................20
Safety valve........................................................................................................................................................................20
Charging CO2....................................................................................................................................................................21
Filter cleaning...................................................................................................................................................................21
Trapped liquid..................................................................................................................................................................21
Leaks in CO2- NH3 cascade systems...........................................................................................................................21
Material compatibility...................................................................................................................................................22
Conclusion.................................................................................................................................................................................22
References.................................................................................................................................................................................22
RA Marketing. 09.2007.mwa
Article
Introduction
Pressure - Temperature
Pressure
[psi] [bar]
14500 1000
1000
CO2
Pressure [bar]
100
145
1.45
R717
R134a
10
10
1
0.1
0,1
0,01
Triple point
Critical point
0.015 0.001
0,001
-120
-120
-184
-60
-60
-76
00
32
60
60
120
120
248
140
Temperature
Figure 1
180 [oC]
180
356 [oF]
Temperature
[psi]
[F]
[psi]
[F]
R 134a
NO
0
1300
40.7
[590]
101.2
[214]
0.004
[0.06]
103
[153]
NO
NO
Table 1
NH3
YES
0
113
132.4
0.06
77.7
CO2
YES
0
1
[1640]
[270]
[0.87]
[108]
(YES)
YES
73.6
31.1
5.18
56.6
[1067]
[87.9]
[75.1]
[69.9]
NO
NO
Article
Characteristics of CO2
[psi]
[bar]
14500 1000
1000
1450
Supercritical
Liquid
100
100
Critical point:
Solid
145
10
10
Vapour
Triple point:
o
56.6C
[69.9F]
5.2 bar [75.1 psi]
14.5
11
-80
-80
-112
Figure 2
-60
-40
-40
-40
00
32
-20
20
40
60
100
40
80
[oC]
104 Temperature
176(Deg.C)
[oF]
Temperature
Density
[Lb/ft3] [kg/m3]
93.6 1500
62.4 1000
Liquid
Critical point:
31.2
+31oC [87.9oF]
73.6 bar [1067 psi]
500
Vapour
Figure 3
0
-40
-40
-40
-40
-20
-20
00
2020
-4
32
-4
32
6868
Saturated
temperature
Saturated
temperature
RA Marketing. 09.2007.mwa
[oC]
4040[oC]
o
104
o [ F]
104 [ F]
Article
CO2 as a refrigerant
Pressure
[psi] [bar]
Pressure (bar-a)
1450 100
Supercritical
100
145
Liquid
Critical point:
Solid -Liquid
10
10
Liquid - Vapour
Solid
Solid - Vapour
14.5
11
Figure 4
Enthalpy
Pressure
bar psi
100
90
80
70
60
1450
1305
1160
1015
870
50
725
40
580
30
435
20
290
Vapour
5.5C [22F]
Subcritical
10
145
73
Figure 5
40C [40F]
Enthalpy
RA Marketing. 09.2007.mwa
Article
CO2 as a refrigerant
(Continued)
Pressure
bar psi
100
90
80
70
60
1450
1305
1160
1015
870
50
725
40
580
30
435
20
290
10
145
73
12C [10F]
Enthalpy
Figure 6
CO2 is most commonly applied in cascade or
hybrid system designs in industrial refrigeration,
because its pressure can be limited to such
extent that commercially available components
like compressors, controls and valves can be
used.
CO2 as a refrigerant in
industrial systems
95C
[203F]
Gas cooling
Pressure
+30C [+86F]
R717
CO2 -R717
Heat exchanger
20C [4F]
15C [+5F]
CO2 compressor
R717
+30C
(12 bar)
+86F
(171 psi)
20C
(1.9 bar)
4F
(28 psi)
Enthalpy
CO2
Pressure
40C [40F]
CO2-receiver
CO2
15C
+5F
(23 bar)
40C
40F
(10 bar)
(333 psi)
(135 psi)
Enthalpy
40C [40F]
Figure 7
RA Marketing. 09.2007.mwa
CO2 evaporator
CO2 as a refrigerant in
industrial systems
(Continued)
Principal diagram
R717 - CO2 cascade system with CO2 hot gas defrosting
+30C [+86F]
Pressure
Article
R717
CO2 - R717 Heat exchanger
20C [4F]
CO2 compressor
15C [+5F]
R717
+30C
(12 bar)
+86F
(171 psi)
20C
(1.9 bar)
4F
(28 psi)
Enthalpy
40C [40F]
CO2
Pressure
CO2 defrost
compressor
CO2-receiver
CO2
+8C [+46F]
Enthalpy
40C [40F]
CO2 evaporator
Figure 8
The CO2 system is a pump circulating system
where the liquid CO2 is pumped from the receiver
to the evaporator, where it is partly evaporated,
before it returns to the receiver. The evaporated
CO2 is then compressed in a CO2 compressor,
and condensed in the CO2-NH3 heat exchanger.
The heat exchanger acts as an evaporator in the
Principal diagram
R717 - CO2 brine system
R717
Pressure
+30C [+86F]
R717
+30C
(12 bar)
+86F
(171 psi)
45C
49F
(0.5 bar)
(7 psi)
Enthalpy
40C [40F]
CO2
CO2
Pressure
CO2-receiver
40C
(10 bar)
40F
(135 psi)
Enthalpy
40C [40F]
CO2 evaporator
Figure 9
RA Marketing. 09.2007.mwa
Article
CO2 as a refrigerant in
industrial systems
(Continued)
Principal diagram
CO2 cascade system with 2 temperature levels
(e.g. supermarket refrigeration)
+30C [+86F]
R717,
R 404A,
R 134a, ......
12C [+10F]
7C [+19F]
CO2
7C
[+19F]
20C
[4F]
Figure 10
Design pressure
DX system
RA Marketing. 09.2007.mwa
Article
Design pressure
(Continued)
Design pressure
bar psi
60 870
50
Design pressure
p + 15%
(barg / psig)
725
p + 10%
(barg / psig)
52 bar
754 psi
40
580
Saturated
pressurep
(bara / psia)
40 bar
580 psi
30
435
20
290
25 bar
363 psi
30
22
20
4
Figure 11
10
0
14
32
Design temperature
10
50
20
68
C
F
5%
Safety valve
10%
Saturated pressure
Figure 12
Safety
10
RA Marketing. 09.2007.mwa
Article
Efficiency
COP
1,86
1,77
1,75
1,42
1,38
1,5
1,78
1,22
1,09
1
0,5
0
Ammonia,
single stage
Ammonia,
two stages
R22, single
stage
R22, two
stage
Ammonia/CO2
cascade
system
Figure 13
PAO
Poly-alpha-olefin oil
(Synthetic Mineral oil)
Solobility
Low (immiscible)
Hydrolysis
Low
Oil separation system Special demand:
High filtration demanded
Challenge
POE
Polyol-ester oil
(Ester oil)
High (miscible)
High affinity to water
No special requirements
Special demand:
Oil drain from low temperature
receiver (oil density lower than
CO2 - opposite NH3)
Oil separation and return system
Long term oil accumulation in
e.g. evaporators
Simple
Table 2
RA Marketing. 09.2007.mwa
11
Article
Comparison of component
requirements in CO2,
ammonia and R134a systems
Compared to ammonia and
R134a, CO2 differs in many
respects. The following
comparison illustrates this fact;
to allow an true comparison,
operational conditions, i.e.,
evaporating temperature,
condensing temperature, are
kept constant.
Wet return
Liquid
Refrigerant
Wet return line
Liquid line
R 134a
[TR]
T
p
Velocity
K
bar
m/s
[F]
[psi]
[ft/s]
Diameter
Area Wet return
mm [inch]
mm2 [inch2]
215
36385
[8.5] 133
[56.40] 13894
[5.2] 69
[21.54] 3774
[2.7]
[5.85]
Velocity
m/s
0.8
[2.6]
[2.6]
0.8
[2.6]
Diameter
Area liquid
Area Wet return
mm [inch]
mm2 [inch2]
mm2 [inch2]
61
2968
39353
[2.4]
[4.6]
[61.0]
36
998
14892
[1.4] 58
[1.55] 2609
[23.08] 6382
[2.3]
[4.04]
[9.89]
[71]
250
CO2
kW
[ft/s]
250
R 717
Capacity
0.8
[71]
250
[71]
41
Leqv = 50 [m] / 194 [ft] - Pump circ.: ncirc = 3 - Evaporating temp.: TE = 40[C] / 40[F]
Table 3
Comparison of pipe cross section area
Dry suction / Liquid lines
Dry suction
Liquid
Refrigerant
Dry suction line
Liquid line
R 134a
250
[71]
R 717
250
CO2
Capacity
kW
[TR]
[71]
250
[71]
T
p
Velocity
K
bar
m/s
[F]
[psi]
[ft/s]
Diameter
mm [inch]
Area Dry suction mm2 [inch2]
168
22134
[6.6] 102
[34.31] 8097
[4.0] 53
[12.55] 2242
[2.1]
[3.48]
Velocity
[2.6]
[2.6]
0.8
[2.6]
[0.8] 35
[0.55] 975
[13.10] 3217
[1.4]
[1.51]
[4.99]
Diameter
Area liquid
Total pipe cross
Area Dry suction
section area
+ liquid
Liquid cross section area
m/s
[ft/s]
mm [inch]
mm2 [inch2]
mm2 [inch2]
0.8
37
1089
23223
0.8
[1.5]
21
[1.69] 353
[36.00] 8450
5
30
Leqv = 50 [m] / 194 [ft] - Evaporating temp.: TE = 40[C] / 40[F] - Condensing temp.: TE = 15[C] / 5[F]
Table 4
12
RA Marketing. 09.2007.mwa
Article
Comparison of component
requirements in CO2,
ammonia and R134a systems
(Continued)
Dry suction
Liquid
Refrigerant
R 134a
Capacity
kW
[TR]
mm2 [inch2]
mm2 [inch2]
mm2 [inch2]
R 717
250 [71]
CO2
[71]
[3.48]
[1.51]
[4.99]
7.2
5
95
%
%
2.6
4
96
5%
5%
95%
95%
1.0
30
70
Liquid
Suction
4%
4%
96%
96%
R134a
30%
30%
70%
70%
CO2
R717
Leqv = 50 [m] / 194 [ft] - Evaporating temp.: TE = 40[C] / 40[F] - Condensing temp.: TE = 15[C] / 5[F]
Table 5
Comparison of compressor displacement
Compressor
Refrigerant
Refrigerant capacity
R 134a
kW
[TR]
250
R 717
[71]
1628 [57489]
13.1
250
CO2
[71]
250
[71]
1092 [38578]
8.8
124
[4387]
1.0
Table 6
Comparison of pressure / subcooling
produced in liquid risers
Refrigerant
Hight of liquid riser H
R 134a
m
3 [9.8]
R 717
3 [9.8]
CO2
[ft]
[9.8]
[psi]
[F]
[4.77]
[1.6]
CO
CO22- reciever
reciever
H
p t
Table 7
RA Marketing. 09.2007.mwa
13
Article
Liquid lines:
In ammonia systems, oil is changed and noncondensables are purged frequently to minimize
the oil, oxygen, water and solid contaminants
that can cause problems.
Liquid CO2
1000
800
600
400
200
Vapour CO2
0
-60
-76
-40
-40
-20
-4
Figure 14
14
0
32
20
68
40
104
60 [ oC]
140 [ F]
Temperature
RA Marketing. 09.2007.mwa
Article
R717
2000
1000
R134a
R404A
CO2
0
-50
-30
-10
Temperature
Figure 15
10
[C]
1000
10
1
-50
Figure 15.1
Vapour
100
-30
-10
Temperature
10
[C]
Figure 16
RA Marketing. 09.2007.mwa
15
Article
CO2 + H2O
vapour phase
40
40
Figure 17
Chemical reactions
CO2 +
Water
CO2 +
ICE
20
4
20 C
68 F
Temperature
0
32
PAO lubricant
16
Article
Removing water
Figure 18
n=3
n=1
1 ppm
RH = 22%
RH >100%
RH = 15.4%
Example:
40/10C - CO2
pump circulating system
with 20 [ppm] water
NH3
Compressor
CO2
Compressor
CO2 receiver
receiver
CO
2
20 ppm
NH3
CO2
1 ppm
Max. solubility in liquid CO 2
@ 40C: 130 [ppm]
@ 10C: 405 [ppm]
RH = 15.4%
RH = 0.25%
Figure 18.1
RA Marketing. 09.2007.mwa
17
Article
Removing water
(Continued)
Example:
40/10C - CO2
DX system
with 20 [ppm] water
20 ppm
RH > 100%
NH3
Compressor
Compressor
Dry suction
Heat exchanger
(condenser)
Evaporator
NH3
Liquid
20 ppm
1 ppm
Max. solubility in liquid CO 2
@ 40C: 130 [ppm]
@ 10C: 405 [ppm]
Figure 18.2
RH = 66.7%
RH = 4.9%
CO2
Compressor
Filter drier
CO2 reciever
CO 2 - NH 3
heat exchanger
CO2
Evaporator
Moisture indicator
Filter drier
Figure 19
Moisture indicator
Liquid
Liquid
RA Marketing. 09.2007.mwa
Article
Removing water
(Continued)
Figure 20
RA Marketing. 09.2007.mwa
19
Article
Miscellaneous features to be
taking into consideration in
CO2 refrigeration systems
Safety valve
CO2s particularly high triple point can cause solid
CO2 to form under certain conditions. Figure
21 shows the expansion processes occurring in
pressure relief valves starting at three different
conditions. If the set pressure of a pressure relief
Pressure
psi
1450
bar
100
+31C [87.9F]
Vapour
50 bar [725 psi]
Vapour
Liquid
20 bar [290 psi]
145
10
0% solid CO2 at
50% solid CO2 at
the triple point
3% solid CO2 at
the triple point
14.5
78.4C [109.1F]
Enthalpy (J)
Figure 21
CO2 expansion - phase changes
Cleaning filers / charging CO2
Pressure
psi
1450
bar
100
+31C [87.9F]
Liquid
20 bar [290 psi]
145
10
56.6C [69.9F]
5.2 bar-a [75.1 psi-a]
14.5
78.4C [109.1F]
Figure 22
If the set pressure of a safety valve in the vapor
phase is 50 bar [725 psi], e.g., the centerline,
the relief line pressure will pass the triple point
and 3% of the CO2 will change into solid as it
continues to relieve. In a worst-case scenario
(e.g., a long relief line with many bends), solid
CO2 may block this line. The most efficient
solution to this problem would be to mount the
safety valve without an outlet line, and relieve
the system directly to the atmosphere. The
phase change of the CO2 does not take place in
the valve, but just after the valve, in this case, in
the atmosphere.
20
Enthalpy (J)
RA Marketing. 09.2007.mwa
Article
Charging CO2
Filter cleaning
Trapped liquid
Reference: 40 [ C] / [ F]
CO2
100%
90%
80%
70%
60%
50%
40%
30%
R134a
R717
20%
10%
0%
40
40
Figure 23
Leaks in CO2- NH3
cascade systems
-20
-20
-4
-4
0
0
32
32
Temperature
Temperature
20
20
68
68
[ooC]
40
40 [o C]
104
104 [[oF]
F]
RA Marketing. 09.2007.mwa
21
Article
Material compatibility
References
[1]
Bondinus, William S
[3]
[6] IoR. Safety Code for Refrigeration Systems Utilizing Carbon Dioxide
The Institute of Refrigeration. 2003.
[7]
22
Vestergaard N.P.
RA Marketing. 09.2007.mwa
Article
RA Marketing. 09.2007.mwa
23
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